JPH0419889B2 - - Google Patents
Info
- Publication number
- JPH0419889B2 JPH0419889B2 JP9262384A JP9262384A JPH0419889B2 JP H0419889 B2 JPH0419889 B2 JP H0419889B2 JP 9262384 A JP9262384 A JP 9262384A JP 9262384 A JP9262384 A JP 9262384A JP H0419889 B2 JPH0419889 B2 JP H0419889B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- ion
- selective membrane
- heat treatment
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000007743 anodising Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 3
- MODGUXHMLLXODK-UHFFFAOYSA-N [Br].CO Chemical compound [Br].CO MODGUXHMLLXODK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 19
- 239000010408 film Substances 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000010407 anodic oxide Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、陽イオンのみを選択的に透過させる
イオン選択膜の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing an ion-selective membrane that selectively allows only cations to pass therethrough.
（従来技術）
近年、特定のイオンのみを選択的に透過させる
ことのできる物質、所謂固体電解質の開発が進め
られており、ナトリウムイオンを選択的に透過さ
せる固体電解質として、β−アルミナが知られて
いる。ところが、このβ−アルミナの実用化を図
るにあたつて、これを薄膜状に形成することが大
きな課題となつているが、未だそのようなイオン
選択膜を製造する方法として適切なものは提案さ
れていない。(Prior art) In recent years, the development of so-called solid electrolytes, which are substances that can selectively transmit only specific ions, has been progressing, and β-alumina is known as a solid electrolyte that selectively transmits sodium ions. ing. However, in trying to put this β-alumina into practical use, forming it into a thin film is a major challenge, and no suitable method for manufacturing such an ion-selective membrane has yet been proposed. It has not been.
（発明の目的）
本発明は、上記の点に鑑みてなされたもので、
その目的は、アルミニウムの陽極酸化皮膜を剥離
熱処理するという簡単な方法で陽イオンを選択透
過し得るイオン選択膜を製造せんとすることにあ
る。(Object of the invention) The present invention has been made in view of the above points, and
The purpose is to produce an ion-selective membrane that can selectively permeate cations by a simple method of heat-treating the anodic oxide film of aluminum.
（発明の構成）
本発明方法は、リン酸水溶液にクエン酸等の有
機酸を添加してなる電解浴を用いてアルミニウム
に陽極酸化処理を施す陽極酸化工程と、陽極酸化
処理後のアルミニウムをブロムメタノール溶液か
らなる剥離浴に浸漬して酸化皮膜を剥離する剥離
工程と、該酸化皮膜を乾燥後850℃以上の温度で
加熱処理する熱処理工程と、熱処理後の酸化皮膜
を苛性アルカリ水溶液に浸漬した後900℃以上の
温度で再加熱処理を施すアルカリ金属拡散工程と
を順次行なうことによつて、陽イオンを選択透過
するイオン選択膜を製造することを特徴としてい
る。(Structure of the Invention) The method of the present invention includes an anodizing process in which aluminum is anodized using an electrolytic bath prepared by adding an organic acid such as citric acid to an aqueous phosphoric acid solution, and an anodizing process in which aluminum is anodized after the anodizing process. A peeling process in which the oxide film is peeled off by immersion in a peeling bath consisting of a methanol solution, a heat treatment process in which the oxide film is dried and then heat treated at a temperature of 850°C or higher, and the oxide film after the heat treatment is immersed in an aqueous caustic alkali solution. The method is characterized in that an ion-selective membrane that selectively permeates cations is manufactured by sequentially performing an alkali metal diffusion step in which a reheating treatment is performed at a temperature of 900° C. or higher.
（作用）
本発明方法では、陽極酸化工程にてリン酸浴を
用いることによつて膜厚100μｍ以上の厚い酸化
皮膜をアルミニウム表面に形成し、この酸化皮膜
を剥離工程にてアルミニウム地金から剥離した
後、熱処理工程にて耐アルカリ性を付与し、酸化
皮膜内へアルカリ金属を拡散せしめるアルカリ金
属拡散工程によつて、陽イオンを選択透過するイ
オン選択膜が得られるのである。(Function) In the method of the present invention, a thick oxide film with a thickness of 100 μm or more is formed on the aluminum surface by using a phosphoric acid bath in the anodizing process, and this oxide film is peeled off from the aluminum base metal in the peeling process. After that, a heat treatment process imparts alkali resistance, and an alkali metal diffusion process in which the alkali metal is diffused into the oxide film yields an ion-selective membrane that selectively permeates cations.
（実施例）
() 陽極酸化工程
20（ｇ／）リン酸水溶液に0.3（ｇ／）ク
エン酸を添加してなる電解浴を用いて純アルミ
ニウム板（縦30mm、横70mm、厚さ0.3mm）を陽
極として60分間直流電解を施す、所謂陽極酸化
処理を行なう。この時の液温は、電解開始時10
℃で、電解終了時約80℃となる如くコントロー
ルし、且つ印加電圧は電解開始時120Vで、開
始後40〜60分の間で160Vとなる如くコントロ
ールする。すると、アルミニウム表面に約
120μｍの膜厚を有する酸化皮膜が形成される。
本工程においては、リン酸浴を用いることによ
つて生成する酸化皮膜の膜厚を大ならしめると
ともに、クエン酸の存在によつて酸化皮膜の孔
径の拡大を図り、膜厚増大に寄与せしめてい
る。なお、クエン酸に代えて、他の適当な有機
酸を用いてもよいことは勿論である。(Example) () Anodic oxidation process A pure aluminum plate (length 30 mm, width 70 mm, thickness 0.3 mm) was prepared using an electrolytic bath made by adding 0.3 (g/) citric acid to a 20 (g/) phosphoric acid aqueous solution. A so-called anodic oxidation process is performed in which direct current electrolysis is performed for 60 minutes using the material as an anode. The liquid temperature at this time is 10
The temperature is controlled to be about 80°C at the end of electrolysis, and the applied voltage is controlled to be 120V at the start of electrolysis and 160V for 40 to 60 minutes after the start. Then, approximately
An oxide film with a thickness of 120 μm is formed.
In this process, the thickness of the oxide film produced is increased by using a phosphoric acid bath, and the pore size of the oxide film is expanded by the presence of citric acid, contributing to the increase in film thickness. There is. Note that, of course, other suitable organic acids may be used in place of citric acid.
() 剥離工程
前記陽極酸化工程にて酸化皮膜を生成された
アルミニウムを30w／ｖ％ブロムメタノール溶
液からなる剥離浴に約３日間浸漬し、アルミニ
ウム地金を溶解して、酸化皮膜（Al2O3を主成
分とする）を得る。() Stripping process The aluminum on which the oxide film was formed in the anodizing process was immersed in a stripping bath consisting of a 30w/v% bromine methanol solution for about 3 days to dissolve the aluminum base metal and remove the oxide film (Al 2 O 3 as the main component) is obtained.
() 熱処理工程
前記剥離工程にて剥離生成された酸化皮膜を
一度乾燥させ、850℃以上の温度で１時間加熱
して耐アルカリ性を付与する。() Heat treatment step The oxide film peeled off in the above peeling step is once dried and heated at a temperature of 850° C. or higher for 1 hour to impart alkali resistance.
() アルカリ金属拡散工程
前記熱処理工程後の酸化皮膜を20w／ｖ％苛
性ソーダ水溶液に数分間浸漬した後、900℃以
上で１時間加熱処理して、酸化皮膜内にナトリ
ウムを拡散せしめる。() Alkali metal diffusion step The oxide film after the heat treatment step is immersed in a 20w/v% caustic soda aqueous solution for several minutes, and then heat treated at 900°C or higher for 1 hour to diffuse sodium into the oxide film.
上記工程により得られたイオン選択膜は、陽
イオンのみを選択的に透過させる性質を有して
いる。 The ion-selective membrane obtained through the above steps has the property of selectively allowing only cations to pass therethrough.
本実施例で得られたイオン選択膜を用いると
図示の如き電池を構成することができる。即
ち、イオン選択膜１によつて画成された二つの
室２，３に0.1N苛性ソーダ水溶液と0.1N塩酸
水溶液とを収容し、両室２，３にグラフアイト
電極４，５を配設する。すると、苛性ソーダ水
溶液側からナトリウムイオン（Na+）が塩酸水
溶液側へ透過して塩化ナトリウムを生成する結
果、塩酸水溶液側が正電位となる一方、苛性ソ
ーダ水溶液側が負電位となり、両電極４，５間
に超電力が生じる。実験によれば、この電池の
超電力は0.512Vであつた。但し、液量40（ml）、
水温30℃とする。 By using the ion selective membrane obtained in this example, a battery as shown in the figure can be constructed. That is, two chambers 2 and 3 defined by the ion selective membrane 1 contain a 0.1N caustic soda aqueous solution and a 0.1N hydrochloric acid aqueous solution, and graphite electrodes 4 and 5 are arranged in both chambers 2 and 3. . Then, sodium ions (Na + ) permeate from the caustic soda aqueous solution side to the hydrochloric acid aqueous solution side and generate sodium chloride. As a result, the hydrochloric acid aqueous solution side becomes a positive potential, while the caustic soda aqueous solution side becomes a negative potential, and there is a gap between the electrodes 4 and 5. Superpower is generated. According to experiments, the superpower of this battery was 0.512V. However, the liquid volume is 40 (ml),
Water temperature is 30℃.
（発明の効果）
叙上の如く、本発明によれば、リン酸浴にて得
られた陽極酸化皮膜を剥離後、熱処理し、更にア
ルカリ金属拡散処理を施すという簡単な製法によ
つて、陽イオンのみを選択的に透過させるイオン
選択膜を製造することができるという優れた効果
がある。(Effects of the Invention) As described above, according to the present invention, an anodic oxide film can be produced by a simple manufacturing method in which the anodic oxide film obtained in a phosphoric acid bath is peeled off, then heat treated, and further subjected to an alkali metal diffusion treatment. An excellent effect is that an ion-selective membrane that selectively transmits only ions can be manufactured.
又、得られたイオン選択膜は、機械的強度を維
持するに十分な膜厚を有しており、実用に十分耐
え得るものである。 Moreover, the obtained ion-selective membrane has a sufficient membrane thickness to maintain mechanical strength, and is sufficiently durable for practical use.
図面は本発明方法で製造されたイオン選択膜の
応用例である電池の模式図である。
１……イオン選択膜、２，３……室、４，５…
…グラフアイト電極。
The drawing is a schematic diagram of a battery which is an application example of the ion selective membrane produced by the method of the present invention. 1... Ion selective membrane, 2, 3... Chamber, 4, 5...
...Graphite electrode.
Claims (1)
てなる電解浴を用いてアルミニウムに陽極酸化処
理を施したものを、ブロムメタノール溶液からな
る剥離浴に浸漬して酸化皮膜を剥離した後、該酸
化皮膜を乾燥後850℃以上の温度で加熱処理し、
次いで苛性アルカリ水溶液に浸漬し、更に900℃
以上の温度で再度加熱処理を施すことを特徴とす
るイオン選択膜の製造方法。1 After anodizing aluminum using an electrolytic bath made by adding an organic acid such as citric acid to an aqueous phosphoric acid solution, the oxide film is removed by immersing it in a stripping bath made of a bromine methanol solution. After drying the oxide film, heat treatment is performed at a temperature of 850°C or higher,
Then, it was immersed in a caustic aqueous solution and further heated to 900℃.
A method for producing an ion-selective membrane, characterized by subjecting it to heat treatment again at a temperature above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9262384A JPS60235609A (en) | 1984-05-08 | 1984-05-08 | Preparation of ion permselective membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9262384A JPS60235609A (en) | 1984-05-08 | 1984-05-08 | Preparation of ion permselective membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60235609A JPS60235609A (en) | 1985-11-22 |
| JPH0419889B2 true JPH0419889B2 (en) | 1992-03-31 |
Family
ID=14059562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9262384A Granted JPS60235609A (en) | 1984-05-08 | 1984-05-08 | Preparation of ion permselective membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60235609A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3542202A1 (en) * | 1985-11-29 | 1987-06-04 | Bernhard Thiel | METHOD FOR PRODUCING SINGLE-WALLED MOLDED PARTS FROM CERAMIC AND MEMBRANE FOR SOUND TRANSDUCER RECEIVED BY THE METHOD |
| GB8602582D0 (en) * | 1986-02-03 | 1986-03-12 | Alcan Int Ltd | Porous anodic aluminium oxide films |
-
1984
- 1984-05-08 JP JP9262384A patent/JPS60235609A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60235609A (en) | 1985-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR920004509B1 (en) | Process of etching aluminium anode foil high voltage electrolytic capacitors | |
| US3632486A (en) | Method and arrangement for continuous etching and anodizing of aluminum | |
| SE8301963L (en) | PROCEDURE FOR THE PREPARATION OF ION EXCHANGE MEMBRANES WITH COATING FOR ELECTRIC LIGHTING | |
| JPH0231489B2 (en) | ||
| US3671410A (en) | Method for making metal oxide membranes | |
| AU1587283A (en) | Electrochemical modification of roughened aluminium surface | |
| JP2000073198A (en) | Method and electrolyte for anodic treatment of valve metal | |
| DE3365930D1 (en) | Method of producing support materials for offset printing plates | |
| JPH0419889B2 (en) | ||
| JPH11172489A (en) | Production of barium titanate coating film | |
| JP3478039B2 (en) | Method of forming electrode foil for aluminum electrolytic capacitor | |
| JPH02235794A (en) | Preparation of aluminum support for printing plate | |
| GB2145738A (en) | Anodizing aluminium foil | |
| JP2638038B2 (en) | Manufacturing method of electrode foil for aluminum electrolytic capacitor | |
| DE3917425C2 (en) | ||
| JPS6211487B2 (en) | ||
| SU714526A1 (en) | Method of manufacturing electrolytic capacitor | |
| SU937534A1 (en) | Composition for molybdenizing steel products | |
| SU1211346A1 (en) | Method of removing active coating off oxide ruthenium-titanium anodes | |
| JPS5831400B2 (en) | How to color aluminum or aluminum alloy | |
| JP2523654B2 (en) | Method for manufacturing electrode foil for aluminum electrolytic capacitors | |
| JPS608317B2 (en) | Black coloring method for aluminum or aluminum alloy | |
| SU866004A1 (en) | Method of electrochemical working of metals | |
| RU1695788C (en) | Method of manufacture of nickel-oxide electrode for alkaline cell | |
| JPS63299309A (en) | Manufacture of electrode foil for aluminum electrolytic capacitor |